KR102067665B1 - Cable comprising crosslinked layer obtained from polymer composition - Google Patents

Abstract

The present invention provides a cable comprising at least one elongated conductor surrounded by at least one crosslinked layer, wherein the crosslinked layer is obtained from a polymer composition comprising a polymer, a crosslinker, and an amine as a crosslinking aid, wherein the amine is It is associated with a cable having a nucleophilic scale value (N) of 14 or greater.

Description

CABLE COMPRISING CROSSLINKED LAYER OBTAINED FROM POLYMER COMPOSITION}

The present invention relates to a cable comprising at least one elongated conductor surrounded by at least one crosslinked layer obtained from the polymer composition.

Hydrogen peroxide crosslinking agents are widely used industrially because they crosslink polymers quickly and effectively. However, such a hydrogen peroxide crosslinking agent generates a considerable amount of low molecular weight by-products during the crosslinking reaction, and these by-products vaporize at a high temperature crosslinking temperature to damage the appearance of the product, and remain in the product even after crosslinking to greatly increase the aging and electrical stability of the product. Decrease. Accordingly, the crosslinking of the polymer composition including the hydrogen peroxide-based crosslinking agent may be performed by using a pressurization device that can prevent the appearance damage caused by the by-products during crosslinking, or degassing to minimize the reduction of the stability of the product by the by-products after crosslinking. ) Has the disadvantage of adding a process.

In order to solve the disadvantage of the hydrogen peroxide-based crosslinking agent, a reactive polymer containing a carboxyl group or an epoxy group may be selected from polyamines, diamine carbamats, organic ammonium salts, and imidazole compounds. A method of crosslinking using a compound such as a crosslinking agent has been proposed. However, the crosslinking rate of these crosslinking agents is often too fast or slow compared to hydrogen peroxide crosslinking agents, and commercial use has been restricted. If the crosslinking rate is too fast, there is a disadvantage in that scorch occurs during the storage, mixing or processing of the composition before forming the product. If the speed is too slow, a long post-curing process at a high temperature may be performed. This is because it has the disadvantage that it is necessary.

Therefore, in order to commercially use the reactive polymer crosslinked material, a technique of controlling the crosslinking rate to an extent corresponding to a hydrogen peroxide-based crosslinking agent is essential.

Various crosslinking agents have been proposed for this purpose. In particular, a composition is disclosed in which a reactive polymer comprising an epoxy group is included with a polycarboxylic acid compound having two or more carboxyl groups and a quaternary ammonium (or phosphonium) salt (US patent 4650834 and 5334666). However, in this case, since a quaternary ammonium (or phosphonium) salt containing a halogen element is included as a crosslinking agent component, there is a problem that it is not suitable for preparing a non-halogen-based polymer crosslinked product.

Thus, there is still a need for a technique that is commercially applicable and capable of providing a crosslinking rate as fast as that of a hydrogen peroxide-based crosslinking agent.

It is an object of the present invention to provide a cable comprising at least one crosslinked layer obtained from a polymer composition capable of providing optimized aging stability while ensuring a fast crosslinking rate.

The present invention to achieve the above object is:

A cable comprising at least one elongated conductor surrounded by at least one crosslinked layer, wherein the crosslinked layer comprises a polymer, a crosslinker, and a polymer composition comprising an amine as a crosslinking aid. Obtained, wherein the amine has a nucleophilic scale value (N) of at least 14, preferably at least 15, more preferably at least 16.

In one preferred embodiment according to the invention, the crosslinking agent in the polymer composition is polyepoxide or polycarboxylic acid.

In another preferred embodiment according to the invention, the polymer is a polymer comprising one or a plurality of carboxyl group (s) or a polymer comprising one or a plurality of epoxy group (s). More specifically, when the polymer containing one or a plurality of carboxyl group (s) is used as the polymer in the present invention, it is preferable that polyepoxide is used as the crosslinking agent. In addition, when a polymer containing one or a plurality of epoxy group (s) is used as the polymer in the present invention, it is preferable that a polycarboxylic acid is used as the crosslinking agent.

Also preferably, the amine is a tertiary amine. More preferably the amine may be one or more selected from:

1,4-diazabicyclo [2.2.2] octane (1,4-diazabicyclo [2.2.2] octane: DABCO), quinuclidine, piperidine, N-methylpiperidine Monocyclic or bicyclic amines selected from (N-methylpiperidine, pyrrolidine, N-methylpyrrolidine, and morpholine);

1,5,7-triazabicyclo [4.4.0] dec-5-ene (1,5,7-Triazabicyclo [4.4.0] dec-5-ene: TBD), 1,2,3,5, 6,7-hexahydroimidazo [1,2-a] pyrimidine (1,2,3,5,6,7-hexahydroimidazo [1,2-a] pyrimidine: TBN), and di-o-tolylguanidine Guanidines selected from (Di-o-tolylguanidine: DOTG);

1,8-diazabicyclo [5.4.0] undec-7-ene (1,8-Diazabicyclo [5.4.0] undec-7-ene: DBU), 1,5-diazabicyclo [4.3. 0] non-5-ene (1,5-diazabicyclo [4.3.0] non-5-ene: DBN), 2-methyl-1,4,5,6-tetrahydropyrimidine (2-Methyl-1, Monocyclic or bicyclic amidine bases selected from 4,5,6-tetrahydropyrimidine; or

Aminopyridines selected from 4- (dimethylamino) pyridine.

Preferably, the amine according to the present invention is included in the composition at 0.05 to 3 parts by weight based on 100 parts by weight of the polymer.

Preferably, the polymer according to the present invention is polyethylene (polyethylenes), polybutadiene (polybutadienes), ethylene-propylene copolymers (ethylene-propylene copolymers), ethylene-α-olefin copolymers (ethylene-α-olefin copolymers), acrylic Acrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, ethylene-vinyl acetate copolymers acrylate copolymers, acrylate-acrylonitrile copolymers, butadiene-acrylonitrile copolymers, butadiene-styrene copolymers, butadiene-acrylonitrile Butadiene-acrylonitrile-acrylate copolymers, styrene- [ethylene- (ethylene-propylene)]-styrene block balls In the group consisting of styrene- [ethylene- (ethylene-propylene)]-styrene block copolymers, and styrene- (ethylene-butylene) -styrene block copolymers Is selected.

Also preferably, the polyepoxides according to the invention are selected from:

a) diethylene glycol diglycidyl ether, diglycidyl ether, diglycidyl ether, ethylene glycol diglycidyl ether, glycerol diglycidyl ether aliphatic compounds selected from the group consisting of diglycidyl ether, neopentyl glycol diglycidyl ether, and propylene glycol diglycidyl ether;

b) cyclic compounds selected from the group consisting of diglycidyl 1,2-cyclohexanedicarboxylate, and triglycidyl isocyanurates ;

c) bisphenol A diglycidyl ether, N, N-diglycidyl-4-glycidyloxyaniline (N, N-diglycidyl-4-glycidyloxyaniline), and 4,4'- Aromatic compounds selected from the group consisting of methylenebis (N, N-diglycidylaniline) (4,4'-methylenebis (N, N-diglycidylaniline));

d) a polymer having a molecular weight of 10,000 g / mol or less having at least two epoxy groups in the polymer main chain, branch or terminal; or

e) a mixture of two or more selected from a) to d).

Preferably, the polycarboxylic acid according to the invention is selected from:

a ') adipic acid, azelaic acid, citric acid, dodecanoic acid, itaconic acid, malic acid, maleic acid Aliphatic compounds selected from the group consisting of sebacic acid, succinic acid, and succinic anhydride;

b ') 1,4-cyclohexanedicarboxylic acid, and cis-4-cyclohexene-1,2-dicarboxylic acid (cis-4-cyclohexene-1,2-dicarboxylic cyclic compounds selected from the group consisting of acid);

c ') 1,3,5-benzenetricarboxylic acid, isophthalic acid, phthalic acid, terephthalic acid, trimellitic acid ), Aromatic compounds selected from the group consisting of phthalic anhydride, and trimellitic anhydride;

d ') a polymer having a molecular weight of 10,000 g / mol or less having at least two carboxyl groups or maleic anhydride in the polymer main chain, branch or terminal; or

e ') at least two mixtures selected from a') to d ').

In one embodiment according to the invention, the polymer composition further comprises an organometallic compound such as, for example, dibutyltin dilaurate, or bismuth-based carboxylate.

In one embodiment, the cable according to the invention may be an electrical cable.

The polymer composition according to the present invention can be crosslinked by a crosslinking process generally used, such as in the case of including a hydrogen peroxide-based crosslinking agent without an additional postcrosslinking process by providing a fast crosslinking speed and a degree of crosslinking. In addition, since by-products are not generated from the cross-linking agent during cross-linking because the non-hydrogen peroxide-based cross-linking agent is used, cross-linking is possible without a separate cross-linking equipment for pressurization, and aging stability and electrical stability by the by-products without applying degassing process after cross-linking Not reduced. Thus, a crosslinked layer with improved aging stability and electrical stability can be obtained.

In addition, since the polymer composition according to the present invention includes an amine and / or an organometallic compound which is a non-halogen-based crosslinking aid, it may be particularly useful for preparing a non-halogen-based crosslinked layer.

Thus, at least one crosslinked layer obtained from the polymer composition according to the invention is used for cables, in particular non-toxic, non-halogen-based cables, for example as insulation, semiconducting and coating / sheath layers, providing improved aging stability, electrical It can give stability and improved insulation properties.

Cables comprising at least one crosslinked layer obtained from the polymer composition according to the invention are not only cables for general power, but also for shipboard, offshore, wind, rolling stock, automotive It can also be used as a cable for mining, and building.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention provides a cable comprising at least one elongated conductor surrounded by at least one crosslinked layer, wherein the crosslinked layer is obtained from a polymer composition comprising a polymer, a crosslinker, and an amine as a crosslinking aid, wherein the amine is A cable having a nucleophilic scale value (N) of 14 or more is provided.

Polymer composition

The polymer composition according to the present invention is a crosslinkable polymer composition, and includes a polymer, a crosslinking agent and an amine.

(A) polymer

The polymer composition according to the invention comprises a polymer, preferably a reactive polymer. In one embodiment according to the invention the composition according to the invention comprises a polymer comprising one or a plurality of carboxyl group (s) as a polymer. In a preferred embodiment, the polymer comprising one or more carboxyl group (s) comprises one or more carboxylic acid (s) or carboxylic anhydride (s) such as maleic anhydride (s) in the polymer backbone or It is a polymer contained in the branch, the polymer is preferably polyethylene (polyethylenes), polybutadiene (polybutadienes), ethylene-propylene copolymers (ethylene-propylene copolymers), ethylene-α-olefin copolymers (ethylene-α-olefin copolymers ), Acrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, ethylene-vinyl acetate-acrylate copolymers vinyl acetate-acrylate copolymers, acrylate-acrylonitrile copolymers, butadiene-acrylonitrile copolymers (butadiene-acrylonitrile copolymers), butadiene-styrene copolymers, butadiene-acrylonitrile-acrylate copolymers, styrene- [ethylene- (ethylene-propylene)]- Selected from styrene- [ethylene- (ethylene-propylene)]-styrene block copolymers and styrene- (ethylene-butylene) -styrene block copolymers Can be. In addition, the polymer may preferably contain at least 0.1% by weight, preferably at least 0.5% by weight, more preferably at least 1% by weight, of the repeating unit including the carboxyl group, based on the total weight of the polymer. have. In addition, the polymer is preferably 30% by weight or less, more preferably 20% by weight or less, more preferably 15% by weight or less, most preferably 10, of the repeating unit including the carboxyl group based on the total weight of the polymer. It may contain up to weight%.

Furthermore, preferably the polymers according to the invention have a molecular weight greater than 5,000 g / mol. In addition, the polymer according to the present invention preferably has a molecular weight of 1,000,000 g / mol or less.

In another embodiment according to the invention, the composition according to the invention comprises a polymer comprising one or a plurality of epoxy group (s) as a polymer. In a preferred embodiment, the polymer comprising one or a plurality of epoxy group (s) is a polymer comprising one or a plurality of epoxy group (s) in the polymer backbone or branch, the polymer is polyethylenes, polybutadiene (polybutadienes), ethylene-propylene copolymers, ethylene-α-olefin copolymers, acrylate copolymers, ethylene-vinyl acetate copolymers vinyl acetate copolymers, ethylene-acrylate copolymers, ethylene-vinyl acetate-acrylate copolymers, acrylate-acrylonitrile copolymers ), Butadiene-acrylonitrile copolymers, butadiene-styrene copolymers mers), and butadiene-acrylonitrile-acrylate copolymers. In addition, the polymer may contain at least 0.1% by weight, preferably at least 0.5% by weight, more preferably at least 1% by weight, of the repeating unit including the epoxy group, based on the total weight of the polymer. In addition, the polymer is preferably 30% by weight or less, more preferably 20% by weight or less, more preferably 15% by weight or less, most preferably 10, of the repeating unit including the epoxy group based on the total weight of the polymer. It may contain up to weight%. Furthermore, preferably the polymers according to the invention have a molecular weight greater than 5,000 g / mol. In addition, the polymer according to the present invention preferably has a molecular weight of 1,000,000 g / mol or less.

In a preferred embodiment, the composition according to the invention may comprise a polymer selected from:

Reactive polymers (C-NBR) containing carboxyl groups in butadiene-acrylonitrile copolymers which are used as wire coating materials due to their excellent resistance to oil, tear, abrasion and inorganic fillers;

-Reactive polymers (C-AEM) containing carboxyl groups in ethylene-acrylate copolymers used as wire coating materials due to their excellent heat, oil, cold resistance, weather resistance and inorganic filler collection properties;

Reactive polymers (C-ACM) containing carboxyl groups in acrylate copolymers used as coating materials for electric wires due to their excellent resistance to heat, oil, cold, weathering and inorganic fillers;

-Reactive polymers containing epoxy groups in ethylene-vinyl acetate-acrylate copolymers, which are used as coating materials for electric wires due to their excellent heat, oil, cold resistance, weather resistance and inorganic filler collection properties (E -AEVA); or

-Ethylene-GMA copolymer (E-GMA) copolymerized with glycidyl methyl methacrylate (GMA) in polyethylene, which is widely used as an insulation material for electric wires due to its excellent insulation properties.

(B) crosslinking agent

The composition according to the present invention includes, as a crosslinking agent, a crosslinking agent that is not a hydrogen peroxide crosslinking agent, that is, a non-hydrogen peroxide crosslinking agent.

In a preferred embodiment, the composition according to the invention comprises polyepoxides as crosslinking agent. The polyepoxide has a compound having two or more epoxy groups in one molecule, or a polymer having two or more epoxy groups in the polymer main chain, branch or terminal, preferably having a molecular weight of 10,000 g / mol or less, more preferably 5,000 g / mol or less It may mean one or more preferably selected from the following:

Diethylene glycol diglycidyl ether, diglycidyl ether, ethylene glycol diglycidyl ether, glycerol diglycidyl ether ), Aliphatic compounds such as neopentyl glycol diglycidyl ether, propylene glycol diglycidyl ether, and the like;

Cyclic compounds such as diglycidyl 1,2-cyclohexanedicarboxylate, triglycidyl isocyanurates, and the like;

Bisphenol A diglycidyl ether, N, N-diglycidyl-4-glycidyloxyaniline, 4,4'-methylenebis (N, N-diglycidyl-4-glycidyloxyaniline) Aromatic compounds such as N, N-diglycidyl aniline) (4,4'-methylenebis (N, N-diglycidylaniline)) and the like;

2 or more epoxy groups such as poly (ethylene glycol) diglycidyl ether and poly (propylene glycol) diglycidyl ether Or a polymer having a terminal molecular weight of 10,000 g / mol or less, more preferably 5,000 g / mol or less, preferably 200 g / mol or more.

More preferably, the polyepoxide is ethylene glycol diglycidyl ether (EGDGE), poly (propylene glycol) diglycidyl ether (poly (propylene glycol) diglycidyl ether), and triglycidyl iso It may be at least one selected from the group consisting of triglycidyl isocyanurates (TGIC).

In another preferred embodiment, the composition according to the invention comprises polycarboxylic acid as crosslinking agent. The polycarboxylic acid may comprise a compound comprising at least two carboxyl groups (ie, carboxylic acids or carboxylic anhydrides such as maleic anhydride) or two or more carboxyl groups or carboxylic anhydrides such as maleic anhydride in a molecule, Branch or terminal, preferably a polymer having a molecular weight of 10,000 g / mol or less, more preferably 5,000 g / mol or less, preferably at least one selected from:

Adipic acid, azelaic acid, citric acid, dodecanoic acid, itaconic acid, malic acid, maleic acid, seba Aliphatic compounds such as sebacic acid, succinic acid, succinic anhydride and the like;

1,4-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, Cyclic compounds such as these;

1,3,5-benzenetricarboxylic acid, isophthalic acid, phthalic acid, terephthalic acid, trimellitic acid, Aromatic compounds such as phthalic anhydride, trimellitic anhydride and the like;

Carboxyl-terminated polybutadiene, carboxyl-terminated butadiene-acrylonitrile copolymer, maleic anhydride-functionalized polybutadiene A polymer having two or more carboxyl groups or maleic anhydride in the polymer main chain, branch or terminal, such as), having a molecular weight of 10,000 g / mol or less, more preferably 5,000 g / mol or less, preferably 200 g / mol or more.

More preferably, the polycarboxylic acid may be at least one selected from the group consisting of adipic acid (ADA), azelaic acid (AZA), and terephthalic acid (TPA).

In one non-limiting embodiment according to the present invention, the crosslinking agent is included in the composition at least 0.1 parts by weight, preferably at least 0.5 parts by weight based on 100 parts by weight of the polymer. In another non-limiting embodiment according to the present invention, the crosslinking agent is included in the composition at 10 parts by weight or less, preferably 5 parts by weight or less based on 100 parts by weight of the polymer.

In a first preferred embodiment of the invention, when the polymer according to the invention is a reactive polymer comprising one or a plurality of carboxyl groups, the polymer composition comprising the polymer comprises polyepoxide as a crosslinking agent.

In a second preferred variant according to the invention, when the polymer according to the invention is a reactive polymer comprising one or a plurality of epoxy group (s), the polymer composition comprising the polymer comprises polycarboxylic acid as a crosslinking agent. .

(C) crosslinking aid

The polymer composition according to the present invention includes an amine having a nucleophilicity measure (N) of 14 or more, preferably a tertiary amine, more preferably a bicyclic amine, as a crosslinking aid.

In the present invention, the nucleophilic scale value is a parameter for measuring nucleophilicity of amines, amino acids, some di- or tri-peptides, pyridine and the like, and methods for calculating the nucleophilic scale value are known in the art. (B. Maji et al., Eur. J. Org. Chem. 2013, 3369), such as, for example,

log k (20 ^o C) = s ( N + E ) (Equation 1)

k = second-order rate constant, M ^-1 s ^-1

s = nucleophile specific slope parameter

N = nucleophilicity parameter

E = electrophilicity parameter

A crosslinking aid comprising an amine having a nucleophilic scale value of at least 14 according to the present invention may be combined with a crosslinking agent according to the invention, in particular a polyepoxide or polycarboxylic acid, in order to improve the crosslinking rate and degree of crosslinking of the crosslinkable composition according to the invention. Can be improved.

In a preferred embodiment, the crosslinking aid may comprise an amine having one or more nucleophilic scale values selected from:

1) 1,4-diazabicyclo [2.2.2] octane (1,4-diazabicyclo [2.2.2] octane) ( N = 18.9 in CH ₃ CN), quinuclidine ( N = 20.5 in CH ₃ CN), piperidine ( N = 18.1 in H ₂ O), N-methylpiperidine ( N = 18.7 in CH ₃ CN), pyrrolidine ( N = 17.2 in H ₂ O), N-methylpyrrolidine ( N = 20.6 in CH ₃ CN), morpholine ( N = 15.6 in H ₂ O), N-methylmorpholine ( Monocyclic or bicyclic amines such as N-methylmorpholine) ( N = 16.8 in CH ₃ CN) and the like;

2) 1,5,7-triazabicyclo [4.4.0] dec-5-ene (1,5,7-Triazabicyclo [4.4.0] dec-5-ene: TBD) ( N = 16.2 in CH ₂ Cl ₂ ), 1,2,3,5,6,7-hexahydroimidazo [1,2-a] pyrimidine (1,2,3,5,6,7-hexahydroimidazo [1,2-a] guanidines such as pyrimidine: TBN) ( N = 16.2 in CH ₂ Cl ₂ ), Di-o-tolylguanidine (DOTG) ( N = 14-15 in CH ₂ Cl ₂ ), and the like;

3) 1,8-diazabicyclo [5.4.0] undec-7-ene (1,8-Diazabicyclo [5.4.0] undec-7-ene: DBU) ( N = 15.3 in CH ₃ CN), 1,5-diazabicyclo [4.3.0] non-5-ene (N = 16.3 in CH ₃ CN), 2-methyl Monocyclic or bicyclic amidine bases such as 2-Methyl-1,4,5,6-tetrahydropyrimidine ( N = 15.2 in CH ₂ Cl ₂ ) (monocyclic or bicyclic amindine bases);

4) aminopyridines such as 4- (dimethylamino) pyridine ( N = 15.8 in CH ₂ Cl ₂ ) and the like.

In a preferred embodiment, the amine having a nucleophilic scale value of at least 14 according to the invention is 1,4-diazabicyclo [2.2.2] octane (1,4-diazabicyclo [2.2.2] octane: DABCO) Or Di-o-tolylguanidine (DOTG).

The polymer composition according to the present invention may further contain an organometallic compound such as dibutyltin dilaurate or bismuth-based carboxylate as a crosslinking aid to further improve its crosslinking rate. It may include.

In one non-limiting embodiment according to the present invention, the crosslinking aid is included in the polymer composition at 0.05 part by weight or more, more preferably 0.1 part by weight or more based on 100 parts by weight of the polymer. In another non-limiting embodiment according to the present invention, the crosslinking aid is included in the polymer composition at 3 parts by weight or less, preferably 1 part by weight or less, based on 100 parts by weight of the polymer.

 (D) other additives

The polymer composition according to the invention may optionally further comprise an organic additive and / or an inorganic additive. Preferably, metal-based and ceramic-based inorganic additives may be included in the polymer composition according to the present invention, for example, to improve filling, physical properties, and flame retardancy. The metal and ceramic inorganic additives are preferably carbon black, calcium carbonate (CaCO ₃ ), talc, clay, graphite, silica, mica, mica, Antimony trioxide, lead oxide, lead oxide, aluminum hydroxide, magnesium hydroxide, magnesium oxide, magnesium oxide, and zinc oxide may be included. In another preferred embodiment, the organic additive can be added, for example, to prevent oxidation, to improve processability, to improve physical properties, to improve dispersibility, or to impart flame retardancy. Preferably, the organic additives include antioxidants, stabilizers, plasticizers, softeners, extenders, pigments, coupling agents and flame retardants. ), And mixtures thereof.

In one non-limiting embodiment, the content of the additive according to the present invention may be up to 500 parts by weight, preferably up to 300 parts by weight based on 100 parts by weight of the polymer.

From the polymer composition Crosslinked  Manufacture of layers

In one embodiment, the crosslinked layer included in the cable according to the invention can be prepared by a process comprising the following steps using the polymer composition described above:

(a) mixing the polymer, the crosslinking agent, and the crosslinking aid and optionally other additives according to the invention at a compounding temperature below the crosslinking temperature, mechanically, for example by a double-roll mill, to produce a crosslinkable polymer composite step. In this step, the compounding temperature may be set based on the glass transition temperature or melting point of the polymer, for example, low crystallinity and glass transition temperature at room temperature, such as C-NBR, C-AEM, C-ACM, E-AEVA. If a lower polymer is used, the temperature is 70 ° C. to 90 ° C., preferably 80 ° C., and a temperature of 10 ° C. higher than its melting point (eg, E-GMA) is used when using a thermoplastic polymer having a relatively high crystallinity such as E-GMA. In the case of GMA, 110 ° C.).

(b) the crosslinking properties of the crosslinkable polymer composite prepared in step (a) (e.g., time required to reach 90% of the minimum and maximum torque value (S _min and S _max ) and the maximum torque value (tc90), etc.) Step to determine. The step may be carried out through a moving die rheometer experiment at a temperature of 170 ° C. to 180 ° C., which is preferably a crosslinking temperature of a polymer including a general hydrogen peroxide crosslinking agent.

(c) forming and crosslinking the crosslinkable polymer composite prepared in step (a) at a crosslinking temperature and pressure determined for tc ₉₀ determined in step (b), for example, using a compression mold. step.

cable

The cable according to the invention comprises at least one elongated conductor surrounded by at least one crosslinked layer. At this time, the crosslinked layer is obtained from the polymer composition described above. In one embodiment, the cable may comprise one or more of the crosslinked layers as an insulating layer, semiconducting layer and / or sheath / coating layer. In particular, the crosslinked layer can be used in cables, in particular non-toxic non-halogen-based cables, to impart improved aging stability and electrical stability.

The cable according to the invention can be used for general power cables. In addition, the cable according to the invention can be used for cables such as shipboard, offshore, wind, rolling stock, automotive, mining, building, etc. have.

Example

Hereinafter, the present invention will be described in more detail with reference to the following non-limiting examples. Moreover, those skilled in the art can apply various modifications to the embodiment according to the present invention within the meaning of the present invention, and the modification is intended to be within the scope of the present invention.

Preparation of polymer composition and crosslinked product thereof according to the present invention and measurement of crosslinking properties

Representative Manufacturing Example

Ethylene-acrylate copolymer containing a carboxyl group (C-AEM, Denka ER A804, including carboxyl groups of about 2wt%), triglycidyl isocyanurates (TGIC, I0428, Tokyo Chemical) Industry Co.), 1,4-diazabicyclo [2.2.2] octane (1,4-diazabicyclo [2.2.2] octane: DABCO, D0134, Tokyo Chemical Industry Co.), dibutyltin dilaurate ( dibutyltin dilaurate: DBTDL, Dabco T-12, Ohsung Polytech Co., Ltd.), PCD-50 (Rhenogran PCD-50, Rhein Chemie), CaCO3 (Hydorcarb 95T, Omya International AG) using a double roll-mill in the formulation ratio shown in Table 1 10 minutes at 80 ℃ to prepare a polymer composition according to the invention. The time taken to reach the minimum and maximum torque value (S _min and S _max ) and 90% of the maximum torque value through experiments using a moving die rheometer at 180 ° C. ( t crosslinking properties such as _c90 ). In addition, the prepared polymer composition was molded and crosslinked using a compression mold at a pressure of about 30 bar at a predetermined crosslinking temperature (180 ° C) during the measured t _c90 to prepare a crosslinked product.

division Abbreviation Compounding ratio (phr) Weight ratio (%) Polymer matrix C-AEM (Denka ER A804) 100 69.4 Crosslinking agent TGIC 2 1.39 Tertiary amine crosslinking aid DABCO 0.5 0.347 Organometallic compounds DBTDL 0.5 0.347 Filler CaCO3 40 27.8 Antioxidant PCD-50 One 0.694

In Table 1, phr means sum of polymers and 100 parts by weight based on parts by weight.

In the same manner as the representative production examples, the polymer composition (Example) according to the present invention, or the polymer composition (Comparative Example) not according to the present invention was prepared using the components and the mixing ratios shown in Table 2 below, and The crosslinking properties were measured and summarized in the following [Table 2]:

*: Means a comparative example not according to the present invention.

The components of the polymer, crosslinking agent and crosslinking aid used in the above examples and comparative examples are described as follows:

C-NBR: a reactive polymer containing a carboxyl group in a butadiene-acrylonitrile copolymer (Nipol NX775 and 1072, each containing 0.083 ephr, 0.075 ephr carboxyl groups, Zeon Co .; "ephr" "Equivalents per hundred parts of rubber," especially C-NBR, "equivalents of carboxyl groups per 100 parts of reactive polymer.",

C-AEM: reactive polymer containing a carboxyl group in an ethylene-acrylate copolymer (Denka ER A403 and A804, including carboxyl groups of about 2 wt.%, Denka),

-C-ACM: reactive polymer containing carboxyl group in acrylate copolymer (Noxtite PA-524 and PA-526, including carboxyl groups of about 1 to 2 wt.%, Unimatec Co. Ltd.)

-E-AEVA: reactive polymer containing epoxy group in ethylene-vinyl acetate-acrylate copolymer (Denka ER 5300 and 8401, including epoxy groups of about 1.5 wt.%, Denka)

E-GMA: ethylene-GMA copolymer copolymerized with glycidyl methyl methacrylate (GMA) in polyethylene (includes LOTADER AX8840, Arkema, 8 wt.% GMA)

-Polyepoxide crosslinker: ethylene glycol diglycidyl ether (EGDGE, E0342, Tokyo Chemical Industry Co.), poly (propylene glycol) diglycidyl ether, poly (propylene glycol) diglycidyl ether, PPG -DGE380 and PPG-DEG640, 406732 and 406740, Sigma-Adrich, triglycidyl isocyanurates (TGIC, I0428, Tokyo Chemical Industry Co.)

Polycarboxylic acid crosslinking agents: adipic acid (ADA, A0161, Tokyo Chemical Industry Co.), azelaic acid (AZA, A0561, Tokyo Chemical Industry Co.), terephthalic acid (TPA) , T0166, Tokyo Chemical Industry Co.)

Polyamine crosslinking agent for comparative example: 4,4'-diaminodiphenylmethane (DADPAM: M0220, Tokyo Chemical Industry Co.), 4,4'-methylenebis (cyclohexylamine) MCHAC: 4,4'-Methylenebis (cyclohexylamine) carbamate, Cheminox AC-6, Unimatec Co. Ltd., 2,2-bis [4- (4-aminophenoxy) phenyl] propane (APP: 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, B1551, Tokyo Chemical Industry Co.)

Amine-based crosslinking aids having a nucleophilic scale value ( N ) of 14 or greater: 1,4-diazabicyclo [2.2.2] octane (1,4-diazabicyclo [2.2.2] octane: DABCO, D0134, Tokyo Chemical Industry Co.), di-o-tolylguanidine (DOTG, Rhenogran DOTG-70, Rhein Chemie)

Amine-based crosslinking aids having a nucleophilic scale value ( N ) of less than 14 for a comparative example: 2-ethyl-4-methylimidazole (EMI: 2-ethyl-4-methylimidazole, E0232, Tokyo Chemical Industry Co. ) ( N = 13.1 in CH ₂ Cl ₂ )

Organometallic compounds: dibutyltin dilaurate (DBTDL, DABCO T-12, Ohsung Polytech Co., Ltd.), bismuth-based carboxylate (BiC, DABCO MB-20, Ohsung Polytech Corporation)

According to Table 2, a polymer composition comprising a combination of a polyepoxide or polycarboxylic acid crosslinking agent and a crosslinking aid according to the present invention having a nucleophilic scale value of 14 or more is currently commercially widely used DADPM, MCHAC, APP Compared with the polymer composition according to the comparative example including a polyamine-based crosslinking agent such as it can be seen that it has a significantly faster crosslinking rate (tc90) and excellent crosslinking degree (ΔS) (run number 2 and 5 in Table 2). In particular, even when the polyamine-based crosslinking agent is used together with the nucleophilic crosslinking aid according to the present invention, the crosslinking performance was not significantly improved (execution number 1 of Table 2), and a nucleophilic scale value of less than 14 with the polyepoxide crosslinking agent Even when the combination of the crosslinking adjuvant is used, the crosslinking performance was not significantly improved (run number 2 of Table 2).

In addition, in the case of including a cross-linking aid having a nucleophilic scale value of 14 or more, the crosslinking rate tended to be faster as the nucleophilic scale value was larger, and the crosslinking degree was increased as the nucleophilic scale value was lower (Table 2 3 and 4 or 5 and 6). In addition, as the number of reactors (i.e., epoxy or carboxyl groups) of the crosslinking agent (polyepoxide or polycarboxylic acid) added is increased (Ex. No. 3, 5 or 8, 9 or 13, 14 of Table 2), the crosslinking agent As the molecular weight of (Table 2, run number 10, 11 or 15, 16), the amount of crosslinking agent is increased (run number 17, 18 in Table 2) tends to increase the crosslinking rate and degree of crosslinking of the polymer composition Seemed. The addition amount of the crosslinking aid having a nucleophilic scale value of 14 or more did not significantly affect the crosslinking rate and the crosslinking degree above the required addition amount (Ex. Nos. 18 and 19 in Table 2), and the organometallic compound in the crosslinking aid was a reactive polymer containing a carboxyl group. When added to the crosslinking, the crosslinking rate was improved (Ex. Nos. 16 and 17 in Table 2), and when added to the reactive polymer containing an epoxy group, the degree of crosslinking was improved (Ex. Nos. 28 and 29 in Table 2).

Preparation of non-halogen flame retardant coating material obtained from the polymer composition according to the present invention

In order to prepare a non-halogen-based flame retardant coating material according to the present invention, first, the components shown in Table 3 were first mixed at 80 ° C. for 10 minutes using a double-roll mill in the following mixing ratio to prepare a polymer composition. For the comparative example, a polymer composition comprising an amine-based crosslinking agent which is currently widely used was prepared in the same manner as in the above method except using the components and the compounding ratios shown in Table 3 below.

Thereafter, crosslinking properties such as Smin, Smax, and tc90 of the prepared polymer composition were determined through a moving die rheometer experiment. Thereafter, the polymer composition was crosslinked under a pressure of 30 bar in a mold at 170 ° C. for a time corresponding to twice the t _c90 at 180 ° C. to prepare a non-halogen flame retardant coating material.

In order to measure the mechanical performances such as tensile strength, elongation at break, etc. of the manufactured coating materials, after making dumbbell-type specimens defined in the DIN 53504.S2 standard, IEC 60811-501 using a universal tensile testing machine Tensile strength and elongation at break were measured under the experimental conditions specified in the specification.

The heating test and oil test were carried out to measure the changed mechanical performance after oil immersion or after heating of the prepared coating material, respectively.

In the heating test, the coating material stabilized for 1 day at room temperature after crosslinking was heat treated in a 120 ^° C. convention oven for 168 hours, and then the changed mechanical performance was tested according to the IEC 60811-501 standard with a universal tensile tester. Measured under conditions. In the oil test, the mechanical performance changed after 7 days of heat treatment at 100 ^o C in accordance with the IEC 60811-404 standard after immersing the coated material stabilized for 1 day at room temperature after crosslinking in IRM 902 oil. Measurements were made under experimental conditions defined by the 60811-501 standard.

The crosslinking properties of the prepared polymer composition, the mechanical performance of the prepared non-halogen flame retardant coating material, and the changed mechanical performance after heating or oil immersion are summarized in Table 3 below.

¹⁾ Rhenofit DDA-70 is a mixture of Diphenylamine derivative (70%) and silica filler (30%).

²⁾ Songnox 1010 is tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Tetrakis [methylene-3- (3,5-di-tert) -butyl-4-hydroxyphenyl) propionate] methane.

³⁾ Rhenogran MMBI-70 is a mixture of methyl-2-mercaptobenzimidazole (70%) and elastomer binder / dispersing agent (30%).

⁴⁾ Struktol WS 180 is a condensation product of fatty acid derivatives and silicones.

As shown in Table 3 above, a polymer composition comprising a combination of a polyepoxide crosslinker according to the present invention and an amine having a nucleophilic scale value of 14 or greater comprises a polymer composition comprising a polyamine crosslinker such as MCHAC, which is currently widely used commercially. The crosslinking rate was much faster than that of. In addition, the mechanical performance of the coating material of the comparative example without the post-crosslinking process was greatly changed after the test due to the additional crosslinking during the heating and oil test, while the coating material according to the present invention did not significantly change the mechanical performance during the heating and oil test. Did.

Therefore, from the results of the comparative examples and examples, the polymer composition according to the present invention has an improved crosslinking speed and degree of crosslinking, and thus can be crosslinked only through a crosslinking process generally applied to a polymer composition including a hydrogen peroxide crosslinking agent without an additional postcrosslinking process. You can see that there is.

Claims (11)

A cable comprising at least one elongated conductor surrounded by at least one crosslinked layer, wherein the crosslinked layer is obtained from a polymer composition comprising a polymer, a crosslinker, and an amine as a crosslinking aid, wherein the amine is at least 14 nucleophilic Cable with a scale value ( N ). The method of claim 1,
And the crosslinker in the polymer composition is a polyepoxide or polycarboxylic acid. The method according to claim 1 or 2,
Wherein said polymer is a polymer comprising one or a plurality of carboxyl group (s) or a polymer comprising one or a plurality of epoxy group (s). The method of claim 1,
The amine is a tertiary amine. The method of claim 1,
A cable, wherein the amine comprises at least one selected from:
1,4-diazabicyclo [2.2.2] octane (1,4-diazabicyclo [2.2.2] octane: DABCO), quinuclidine, piperidine, N-methylpiperidine Monocyclic or bicyclic amines selected from (N-methylpiperidine, pyrrolidine, N-methylpyrrolidine, and morpholine);
1,5,7-triazabicyclo [4.4.0] dec-5-ene (1,5,7-Triazabicyclo [4.4.0] dec-5-ene: TBD), 1,2,3,5, 6,7-hexahydroimidazo [1,2-a] pyrimidine (1,2,3,5,6,7-hexahydroimidazo [1,2-a] pyrimidine: TBN), and di-o-tolylguanidine Guanidines selected from (Di-o-tolylguanidine: DOTG);
1,8-diazabicyclo [5.4.0] undec-7-ene (1,8-Diazabicyclo [5.4.0] undec-7-ene: DBU), 1,5-diazabicyclo [4.3. 0] non-5-ene (1,5-diazabicyclo [4.3.0] non-5-ene: DBN), 2-methyl-1,4,5,6-tetrahydropyrimidine (2-Methyl-1, Monocyclic or bicyclic amidine bases selected from 4,5,6-tetrahydropyrimidine; or
Aminopyridines selected from 4- (dimethylamino) pyridine. The method of claim 1,
Wherein the composition comprises from 0.05 part by weight to 3 parts by weight based on 100 parts by weight of the polymer. The method of claim 1,
The polymer is polyethylene (polyethylenes), polybutadiene (polybutadienes), ethylene-propylene copolymers (ethylene-propylene copolymers), ethylene-α-olefin copolymers (ethylene-α-olefin copolymers), acrylate copolymers (acrylate copolymers) , Ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, ethylene-vinyl acetate-acrylate copolymers, acrylates- Acrylate-acrylonitrile copolymers, butadiene-acrylonitrile copolymers, butadiene-styrene copolymers, butadiene-acrylonitrile-acrylate copolymers -acrylonitrile-acrylate copolymers), styrene- [ethylene- (ethylene-propylene)]-styrene block copolymers (styrene- [ethylene- (ethyle) ne-propylene)]-styrene block copolymers), and styrene- (ethylene-butylene) -styrene block copolymers. The method of claim 2,
The cable, wherein polyepoxide is selected from:
a) Diethylene glycol diglycidyl ether, diglycidyl ether, diglycidyl ether, ethylene glycol diglycidyl ether, glycerol diglycidyl ether aliphatic compounds selected from the group consisting of diglycidyl ether, neopentyl glycol diglycidyl ether, and propylene glycol diglycidyl ether;
b) cyclic compounds selected from the group consisting of diglycidyl 1,2-cyclohexanedicarboxylate, and triglycidyl isocyanurates ;
c) bisphenol A diglycidyl ether, N, N-diglycidyl-4-glycidyloxyaniline (N, N-diglycidyl-4-glycidyloxyaniline), and 4,4'- Aromatic compounds selected from the group consisting of methylenebis (N, N-diglycidylaniline) (4,4'-methylenebis (N, N-diglycidylaniline));
d) a polymer having a molecular weight of 10,000 g / mol or less having at least two epoxy groups in the polymer main chain, branch or terminal; or
e) a mixture of two or more selected from a) to d). The method of claim 2,
The polycarboxylic acid is selected from:
a ') adipic acid, azelaic acid, citric acid, dodecanoic acid, itaconic acid, malic acid, maleic acid Aliphatic compounds selected from the group consisting of sebacic acid, succinic acid, and succinic anhydride;
b ') 1,4-cyclohexanedicarboxylic acid, and cis-4-cyclohexene-1,2-dicarboxylic acid (cis-4-cyclohexene-1,2-dicarboxylic cyclic compounds selected from the group consisting of acid);
c ') 1,3,5-benzenetricarboxylic acid, isophthalic acid, phthalic acid, terephthalic acid, trimellitic acid ), Aromatic compounds selected from the group consisting of phthalic anhydride, and trimellitic anhydride;
d ') a polymer having a molecular weight of 10,000 g / mol or less having at least two carboxyl groups or maleic anhydride in the polymer main chain, branch or terminal;
e ') at least two mixtures selected from a') to d '). The method of claim 1,
And the polymer composition further comprises an organometallic compound. The method of claim 1,
Cable which is power cable.